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Coordination chemistry of [2 + 2] Schiff-base macrocycles derived from the dianilines [(2-NH2C6H4)2X] (X = CH2CH2, O): structural studies and ROP capability towards cyclic esters

Wang, Kuiyuan; Prior, Timothy J.; Hughes, David L; Arbaoui, Abdessamad; Redshaw, Carl

Authors

Kuiyuan Wang

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Dr Tim Prior T.Prior@hull.ac.uk
Senior Lecturer in Inorganic Chemistry

David L Hughes

Abdessamad Arbaoui

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Professor Carl Redshaw C.Redshaw@hull.ac.uk
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry



Abstract

Reaction of the [2 + 2] Schiff-base macrocycles {[2-(OH)-5-(R)-C6H2-1,3-(CH)2][CH2CH2(2-C6H4N)2]}2(R = Me, L1H2;tBu, L2H2) with FeBr2afforded the complexes [FeBr(L1H2)]2[(FeBr3)2O]·2MeCN (1·2MeCN), [FeBr(L2H2)][X] (X = 0.5(FeBr3)2O,2·0.5MeCN, X = Br,3·5.5MeCN), respectively. Reaction of L2H2with [KFe(OtBu)3(THF)] (formedin situfrom FeBr2and KOtBu), following work-up, led to the isolation of the complex [Fe(L2)(L2H)]·3MeCN (4·3MeCN), whilst with [CuBr2] afforded [CuBr(L2H2)][CuBr2]·2MeCN (5·2MeCN). Attempts to form mixed Co/Ti species by reaction of [CoBrL2][CoBr3(NCMe)] with TiCl4resulted in [L2H4][CoBr4]·2MeCN (6·2MeCN). Use of the related oxy-bridged Schiff-base macrocycles {[2-(OH)-5-(R)-C6H2-1,3-(CH)2][O(2-C6H4N)2]}2(R = Me, L3H2;tBu, L4H2) with CoBr2led to the isolation of the complexes [(CoBr)2(L3)]·2C3H6O (7·2C3H6O), [Co(NCMe)2(L4H2)][CoBr4]·5MeCN (8·5MeCN), [Co(NCMe)6][CoBr3(MeCN)]2·2MeCN (9·2MeCN). For comparative structural/polymerisation studies, the complexes {CoBr(NCMe)L5}2·2MeCN (10·2MeCN) and [Co(NCMe)2L5]2[CoBr3(NCMe)]2(11), [FeBr(NCMe)L5]2·2MeCN (12·2MeCN) where L5H = 2,6-(CHO)2-4-tBu-C6H2OH, as well as the chelate-free salt [Fe(NCMe)6][FeBr3OFeBr3] (13) have been isolated and structurally characterized. The ability of these complexes to act as catalysts for the ring opening polymerisation (ROP) of ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) was investigated, as well as co-polymerisation of ε-CL withrac-lactide (r-LA) andvice versa.

Citation

Wang, K., Prior, T. J., Hughes, D. L., Arbaoui, A., & Redshaw, C. (2021). Coordination chemistry of [2 + 2] Schiff-base macrocycles derived from the dianilines [(2-NH2C6H4)2X] (X = CH2CH2, O): structural studies and ROP capability towards cyclic esters. Dalton Transactions : an international journal of inorganic chemistry, 50(23), 8057-8069. https://doi.org/10.1039/d1dt00711d

Journal Article Type Article
Acceptance Date May 4, 2021
Online Publication Date May 4, 2021
Publication Date Jun 21, 2021
Deposit Date May 10, 2021
Publicly Available Date May 10, 2021
Journal Dalton Transactions
Print ISSN 1477-9226
Electronic ISSN 1477-9234
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 50
Issue 23
Pages 8057-8069
DOI https://doi.org/10.1039/d1dt00711d
Keywords Schiff-base; Macrocycle; Iron; Cobalt; Copper; Structures; Ring opening polymerisation
Public URL https://hull-repository.worktribe.com/output/3767567

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